TW202102572A - Solvent-based compositions - Google Patents

Abstract

Embodiments of the present disclosure are directed towards solvent-based compositions that include a reaction product formed by reacting a polyol and an aminopolycarboxylic compound.

Description

Solvent-based composition

The embodiments of the present disclosure are directed to solvent-based compositions. More specifically, the embodiments are directed to solvent-based compositions, which include reaction products formed by reacting polyols with amino polycarboxylic acid compounds.

The solvent-based composition may include polyols, isocyanates, and solvents as well as other possible components. For example, when a solvent-based composition is used for adhesive applications, it can be contacted with two substrates so that the polyol and isocyanate can react with each other to form a cured product and form a bond between the two substrates. For example, when a solvent-based composition is used in coating applications, it can be contacted with a substrate so that the polyol and isocyanate can react with each other to form a cured product.

The present disclosure provides solvent-based compositions, the compositions including: a reaction product prepared by reacting a polyol with an amino polycarboxylic acid compound; an isocyanate; and a solvent.

The above summary of the present disclosure is not intended to describe the disclosed embodiments or every implementation of the present invention. The following embodiments more specifically illustrate exemplary embodiments. In several places throughout the application, guidance is provided through a list of examples, which can be used in different combinations. In each case, the list is only used as a representative group and should not be construed as an exclusive list.

The reaction product of polyol and amino polycarboxylic acid compound is disclosed herein. The reaction product can be used in a solvent-based composition that can desirably provide one or more improved properties.

For example, a solvent-based composition that includes the reaction product can provide an improvement (that is, an increase) on day 7 compared to other compositions that include a polyol similar to the polyol used to make the reaction product T-Peel bonding strength. The increased T-peel bond strength on day 7 indicates greater bond strength, which is desirable for many applications.

In addition, solvent-based compositions that include reaction products can provide improved (ie, increased) retort bag values compared to other compositions that include polyols similar to the polyols used to make the reaction products. When the packaged product made with the solvent-based composition disclosed herein is used in combination with a consumer product, the improved retort pouch value can indicate greater adhesion strength. For many applications, greater adhesion strength is required.

In addition, solvent-based compositions containing reaction products can provide improved (eg, faster) curing compared to other compositions that include polyols similar to the polyols used to make the reaction products. Advantageously, relatively faster curing can help provide faster primary aromatic amine (PAA) decay. For many applications (such as those related to food regulatory compliance), faster primary aromatic amine decay may be required.

As mentioned, the reaction product of a polyol and an amino polycarboxylic acid compound is disclosed herein. As used herein, "amino polycarboxylic acid compound" includes its derivatives and/or structural analogs. One or more embodiments specify that the amino polycarboxylic acid compound is an ethylenediaminetetraacetic acid compound. Examples of amino polycarboxylic acid compounds, derivatives and/or structural analogs include, but are not limited to, ethylenediaminetetraacetic anhydride, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic dianhydride, 4,4'-( Propane-1,2-diyl)bis(morpholine-2,6-dione), 4,4'-(propane-1,3-diyl)bis(morpholine-2,6-dione) and 4,4'-(oxybis(ethane-2,1-diyl))bis(morpholine-2,6-dione). One or more embodiments of the present disclosure provide that the ethylenediaminetetraacetic acid compound can be selected from ethylenediaminetetraacetic anhydride, ethylenediaminetetraacetic acid, and combinations thereof.

。Ethylenediaminetetraacetic acid dianhydride can be represented by the following formula:

.

The embodiments of the present disclosure provide that the polyol that reacts with the amino polycarboxylic acid compound can be a polyether polyol, a polyester polyol or a combination thereof.

The polyol can be prepared by a known process (for example, by using known components, known equipment, and known reaction conditions). Polyols are commercially available.

Examples of commercially available polyols include, but are not limited to, polyols sold ^{under the trade names VORANOL™} , TERCAROL ^™ , MOR-FREE ^™ , PRIPLAST ^™ and VORATEC ^{™ and others.}

One or more embodiments of the present disclosure provide that the polyol may include polyether polyol. The polyether polyol can be prepared by a known process. For example, polyether polyols can be prepared by alkoxylation of starter compounds. Alkoxylation is the anionic addition polymerization of at least one alkylene oxide (for example, ethylene oxide, 1,2-propylene oxide, or 1,2-butylene oxide). A starter compound that can be referred to as an initiator is any organic compound that is alkoxylated in the polymerization reaction. The initiator may contain 2 or more hydroxyl groups and/or amine groups. Mixtures of starter compound/initiator can be used. Examples of initiator compounds include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8 -Caprylyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose and any of these alkoxylates (especially ethoxylates) And/or propoxylates), polyamines and dialkanolamines or trialkanolamines. If several epoxides are used to synthesize the polyether polyol, the latter can have any arrangement of the desired oxyalkylene moieties. It can be a homopolymer (if only one epoxide is used), a copolymer, a random copolymer, a capped polymer, or a polymer synthesized with a mixture of different epoxides to obtain the required primary hydroxyl content.

One or more embodiments of the present disclosure provide that the polyol may include polyester polyol. Polyesters can be prepared from, for example, organic dicarboxylic acids having 2 to 12 carbon atoms (including aromatic dicarboxylic acids having 8 to 12 carbon atoms) and polyols (including diols having 2 to 12 carbon atoms) -Polyol. Examples of suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, ortho Phthalic acid, isophthalic acid, terephthalic acid and isomerized naphthalenedicarboxylic acid. The dicarboxylic acids can be used alone or mixed with each other. Free dicarboxylic acids can be replaced by corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters or dicarboxylic acid anhydrides of alcohols having 1 to 4 carbon atoms. Some specific examples may utilize dicarboxylic acid mixtures (which include succinic acid, glutaric acid, and adipic acid in a ratio of, for example, 20 to 35:35 to 50:20 to 32 parts by weight), and phthalic acid and/ Or a mixture of phthalic anhydride and adipic acid; phthalic acid or a mixture of phthalic anhydride, isophthalic acid and adipic acid; or dicarboxylic acid of succinic acid, glutaric acid and adipic acid Acid mixture; and mixture of terephthalic acid and adipic acid; or dicarboxylic acid mixture of succinic acid, glutaric acid and adipic acid. Examples of diols and polyols are ethylene glycol, diethylene glycol, 1,2-propanediol and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-Hexanediol, 1,10-decanediol, glycerin, trimethylolpropane and others. Some specific examples specify ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture of at least two of these glycols, especially A mixture of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. In addition, polyester-polyols prepared from lactones (such as ε-caprolactone) or hydroxycarboxylic acids (such as ω-hydroxycaproic acid and hydrobenzoic acid) can also be used.

The polyester polyol can be prepared by, for example, polycondensing an organic polycarboxylic acid and/or its derivative and a polyol with a molar ratio of 1:1 to 1:1.8 (for example, 1:1.05 to 1:1.2).

The weight average molecular weight of the polyol used to prepare the reaction product disclosed herein may be 300 to 12,000 g/mol. Including all individual values and sub-ranges from 300 to 12,000 g/mol; for example, the weight average molecular weight of polyols can be from 300, 400, 500, 750, or 1000 to 12,000, 10,000, 8000, 5000, or 3000 g/mol Upper limit.

The average functionality (ie, hydroxyl functionality) of the polyol used to prepare the reaction product disclosed herein may be 1.5 to 5.0. Including all individual values and sub-ranges from 1.5 to 5.0; for example, the average functionality of polyols can be from the lower limit of 1.5, 1.7 or 2.0 to the upper limit of 5.0, 4.0 or 3.0.

It can be prepared by reacting the polyol and the amino polycarboxylic acid compound with the molar ratio of the number of moles of the hydroxyl group of the polyol from 100:0.5 to 100:10 and the number of moles of the functional group of the amino polycarboxylic acid compound. The reaction product of polyol and amino polycarboxylic acid compound. {3} Including all individual values and sub-ranges of the molar number of the polyol hydroxyl group from 100:0.5 to 100:10 to the molar number of the functional group of the amino polycarboxylic acid compound; for example, 100:0.5, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9 or 100:10 molar number of polyol hydroxyl group and amino polycarboxylic acid compound The molar ratio of the molar number of the functional group allows the polyol to react with the amino polycarboxylic acid compound. Amino polycarboxylic acid compound functional groups include dianhydrides, monoanhydride diacids, tetraacids, and combinations thereof.

Known equipment and reaction conditions can be used to form the reaction product. For example, the reactants (ie, polyol and amino polycarboxylic acid compound) can be heated to any desired temperature for a prescribed time sufficient to achieve the desired chemical/physical conversion. As an example, the reaction product may be formed at a temperature of 50° C. to 200° C.; the reaction may occur (for example, maintain) for about 5 minutes to about 48 hours; and the reaction may be carried out in an inert environment (such as a nitrogen environment). Depending on the situation, the reaction product can be formed by the catalyst.

The reaction product of the polyol and the amino polycarboxylic acid compound may include 0.03 to 10.0% by weight of the unit derived from the amino polycarboxylic acid compound based on the total weight of the reaction product. Including 0.03 to 10.0% by weight of all individual values and sub-ranges of units derived from the amino polycarboxylic acid compound; for example, the reaction product may include the lower limit of 0.03, 0.05, 0.08, or 1.0 to 10.0, based on the total weight of the reaction product, The upper limit of 8.0, 6.0, or 5.0% by weight of the unit derived from the amino polycarboxylic acid compound.

The embodiments of the present disclosure provide a solvent-based composition, which includes a reaction product of a polyol and an amino polycarboxylic acid compound, an isocyanate, and a solvent. The solvent-based composition can be prepared (for example, mixed) using known conditions and known equipment, and the known conditions and known equipment can vary for different applications.

The isocyanate may be a polyisocyanate. As used herein, "polyisocyanate" refers to a molecule having an average of greater than 1.0 isocyanate groups per molecule, for example, an average isocyanate functionality of greater than 1.0.

The isocyanate may be, for example, an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an arylaliphatic polyisocyanate, an aromatic polyisocyanate, or a combination thereof. Examples of isocyanates include, but are not limited to, toluene 2,4-/2,6-diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), polymeric MDI, triisocyanate nonane (TIN), Naphthyl diisocyanate (NDI), 4,4'-diisocyanato dicyclohexylmethane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) IPDI), butylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecyl diisocyanate, 1,4-diisocyanate cyclohexane, 4,4'-diisocyanate-3,3'-dimethyldicyclohexylmethane, 4,4'- Diisocyanate-2,2-dicyclohexylpropane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1,3-diisooctylcyanate 4-methylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl) Base) cyclohexane and its combination and others. In addition to the isocyanates mentioned above, partial modifications including uretdione, isocyanurate, carbodiimide, ureidoimine, allophanate or biuret structures and combinations thereof can be used. Quality polyisocyanate.

Isocyanates can be polymeric. As used herein, when describing isocyanates, "polymeric" refers to higher molecular weight homologs and/or isomers. For example, polymeric methylene diphenyl isocyanate refers to the higher molecular weight homologues and/or isomers of methylene diphenyl isocyanate.

The isocyanate can be a prepolymer. For example, the isocyanate can be an isocyanate-terminated prepolymer, such as an isocyanate-terminated polyurethane prepolymer. Prepolymers can be prepared by reacting isocyanates with polyols.

As mentioned, the average functionality of the isocyanate can be greater than 1.0 isocyanate groups/molecule. For example, the average functionality of the isocyanate can be 1.75 to 3.50. Including all individual values and sub-ranges from 1.75 to 3.50; for example, the average functionality of isocyanate can be from the lower limit of 1.75, 1.85 or 1.95 to the upper limit of 3.50, 3.40 or 3.30.

The isocyanate equivalent of isocyanate can be 84 g/eq to 1000 g/eq. Including all individual values and sub-ranges from 84 to 1000 g/eq; for example, the isocyanate equivalent of isocyanate can be from the lower limit of 84, 95, 115, 125, 135 or 145 to 1000, 800, 600, 500, 300, The upper limit of 290 or 280 g/eq.

The isocyanate can be prepared by a known process. For example, polyisocyanates can be prepared by the following steps: phosgenation of the corresponding polyamines simultaneously form polyamine chloride methyl esters and pyrolyze them to obtain polyisocyanates and hydrogen chloride, or by a phosgene-free process (such as by By reacting the corresponding polyamine with urea and alcohol to obtain polyurethane) and pyrolyzing it to obtain, for example, polyisocyanate and alcohol.

Isocyanates are commercially available. Examples of commercially available isocyanate and/or NCO-terminated prepolymers include but are not limited to isocyanates available under the ^{trade names MOR-FREE TM} , VORANATE ^TM and PAPI ^{TM from The Dow Chemical Company and others} Isocyanates are commercially available.

Isocyanates can be used so that the isocyanate index of the solvent-based composition is in the range of 0.9 to 1.6. The isocyanate index can be measured as the equivalent of isocyanate divided by the total equivalent of isocyanuric acid-reactive components (such as isocyanate-reactive hydrogen) of the solvent-based composition, which increases exponentially. In other words, the isocyanate index can be measured as the ratio of isocyanate groups to isocyanate reactive hydrogen. Including all individual values and sub-ranges from 0.9 to 1.6; for example, the isocyanate index of a solvent-based composition can be from the lower limit of 0.9, 1.0, 1.05, or 1.1 to the upper limit of 1.6, 1.5, 1.45, or 1.4.

The solvent-based composition includes a solvent. As used herein, "solvent-based composition" refers to a composition that includes at least 10% by weight of solvent based on the total weight of the reaction product, isocyanate, and solvent. Based on the total weight of the reaction product, isocyanate, and solvent, the solvent may be 10% to 80% by weight of the solvent-based composition. Including all individual values and sub-ranges from 10% to 80% by weight; for example, based on the total weight of the reaction product, isocyanate and solvent, the solvent can be from 10, 12, or 15% by weight to 80, 75, or The upper limit of 70% by weight.

The solvent may be an organic solvent. The solvent may be a hydrocarbon solvent. The solvent may be an aromatic solvent. Examples of solvents include, but are not limited to, acetone, methyl ethyl ketone, methyl butyl ketone, other ketones, ethyl acetate, butyl acetate, other alkyl acetates, toluene, xylene, with six to sixteen Other aromatic solvents of carbon atoms and combinations thereof.

The solvent-based composition may include a catalyst, such as known catalysts used to form polyurethanes. Examples of catalysts include aluminum catalysts, bismuth catalysts, tin catalysts, vanadium catalysts, zinc catalysts, zirconium catalysts, titanium catalysts, amine catalysts, and combinations thereof. One or more embodiments specify that the catalyst is selected from the group consisting of dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylpyruvate, dibutyltin dithiolate, dibutyltin dioctoate, dibutyltin dimaleate, Dibutyltin acetonylpyruvate, dibutyltin oxide and combinations thereof. When a catalyst is used, it can be 0.001 parts per million (ppm) to 100 ppm based on the total weight of the solvent-based composition. For example, the catalyst may be 0.005 ppm to 10 ppm based on the total weight of the solvent-based composition.

The embodiments of the present disclosure provide that the solvent-based composition may include one or more other components, such as known components used with adhesive compositions and/or known components used with, for example, coating compositions. Different other components and/or different amounts of other components can be used for various applications. Examples of other components include polyols, surfactants, chelating agents, crosslinking agents, chain extenders, antioxidants and combinations thereof, as well as other known components.

Advantageously, a solvent-based composition can be applied to the material. For example, the solvent-based composition can be applied to the first material and the second material can be contacted with the solvent-based composition; subsequently, the solvent-based composition can be cured to form a laminate. In addition, a solvent-based composition can be applied to the first material and then the composition can be cured to form a coating. The solvent-based composition can be coated by a known process (for example, by using known components, known equipment, and known application conditions) (such as gravure lamination, elastic relief lamination, etc.). In addition, the components of the solvent-based composition can be coated on different substrates and then laminated together.

The solvent-based composition disclosed herein can be cured. For example, the reaction product of a polyol and an amino polycarboxylic acid compound and an isocyanate can react with each other to form a cured product. Known curing conditions (such as temperature, humidity, and duration) can be used to cure the solvent-based compositions disclosed herein.

Advantageously, compared to other compositions that include polyols similar to the polyols used to make the reaction product, the solvent-based compositions disclosed herein provide improvements that can, for example, provide improvements on day 7 during curing. T-Peel bonding strength. As mentioned, the increased T-peel bond strength on day 7 indicates greater bond strength. This greater adhesion strength can desirably help provide a greater seal for products made with the solvent-based compositions disclosed herein.

Advantageously, the solvent-based compositions disclosed herein can provide improved retort pouch values when cured, for example, compared to other compositions that include polyols similar to the polyols used to make the reaction product. When encapsulated products made from the solvent-based compositions disclosed herein are used in combination with consumer products such as sauces and other consumer products, the improved retort pouch value indicates greater adhesion strength. In other words, the improved retort bag value can indicate the resistance of the desired improved consumer product to packaging failure.

In addition, solvent-based compositions that include reaction products can provide improved (eg, faster) curing compared to other compositions that include polyols similar to the polyols used to make the reaction products. Advantageously, relatively faster curing can help provide faster primary aromatic amine (PAA) decay. For many applications (such as those related to food regulatory compliance), faster primary aromatic amine decay may be required.

As used herein, a polyol similar to the polyol used to make the reaction product refers to the same polyol as the polyol used to make the reaction product; or a weight average molecular weight compared to the polyol used to make the reaction product It is a polyol with + 10% and an average hydroxyl functionality of + 10%.

The examples stipulate that the solvent-based composition can be used with various materials (such as substrates). Examples of materials that can be used with the solvent-based compositions disclosed herein include polymeric materials such as polyethylene terephthalate, polyethylene, polypropylene, and combinations thereof. The polymeric material can be, for example, a film. The examples specify that the materials that can be used with the solvent-based composition may include metals, such as foils or metallized films. Foil and metallized films are well known. For example, the polymeric material can be pre-treated (such as by corona treatment and plasma treatment) before metallization. Then, the metalization can be performed by a physical vapor deposition process. In this type of process, the metal is heated and evaporated under vacuum. The metal then condenses on the polymeric material to form a metalized film. Examples of suitable metals include, but are not limited to, aluminum, nickel, chromium, and combinations thereof. The examples specify that solvent-based compositions can be used for, for example, film-to-film lamination and film-to-foil lamination. Instance

In the examples, various terms and names of materials are used, including, for example, the following:

Amino polycarboxylic acid compound (ethylenediaminetetraacetic acid dianhydride; available from Aldrich);

Polyol #1 (polyester polyol; the average functionality of polyester polyol is 2.0 and the weight average equivalent is 2000 g/mol);

MOR-FREE CR9-101 (isocyanate; available from The Dow Chemical Company);

MOR-FREE C-33 (aliphatic isocyanate; available from The Dow Chemical Company);

Methyl ethyl ketone (solvent; available from Aldrich);

Ethyl acetate (solvent; available from Aldrich);

Metallized PET film (metallized 48 g PET film; available from Filmquest Group); PET film (48 LBT; polyester film [poly(ethylene glycol-terephthalate)]; available from DuPont ); PET/foil laminated film (PET aluminum foil film; obtained from FILM TECH); low-density polyethylene film (GF-19 film; high-lubricity low-density film; thickness 1.5 mil; obtained from Berry Plastics Company (Berry Plastics Corp).

The laboratory-synthesized polyester polyol was prepared as follows. Add 1,6-hexanediol (1012.3 grams; available from Aldrich), neopentyl glycol (494.9 grams; available from Aldrich) and adipic acid (1492.8 grams; obtained from Aldrich) to the container under a nitrogen atmosphere. (From Aldrich); while stirring, slowly heat the contents of the container from about 25°C to about 100°C. Then, the contents of the container are slowly heated to about 190°C and kept at this temperature until the acid value is about 10 mg KOH/g. Next, the contents of the container were cooled to about 125°C and titanium isopropoxide (0.03 g; available from Aldrich) was added to the container and the contents of the container were maintained at about 125°C for 30 minutes. Then, slowly heat the contents of the container to about 190°C and keep it at this temperature until the acid value is about 1 mg KOH/g; if the acid value needs to be reduced, apply a vacuum (435 mm Hg). Then, the contents of the container were cooled to about 125°C and filtered to provide a polyester polyol synthesized in the laboratory.

Example 1 was prepared as follows, which is a reaction product of polyol and ethylenediaminetetraacetic acid dianhydride. The laboratory-synthesized polyester polyol (99 grams) was added to the container and dried under flowing nitrogen at approximately 105°C for 60 minutes. Next, add ethylenediaminetetraacetic dianhydride (1 gram) to the container, and slowly heat the contents of the container to 170°C and maintain it at this temperature for about 3 hours; then, slowly heat the contents of the container To 180°C and maintain at this temperature for about 30 minutes. Then, the contents of the container were cooled to about 90°C and filtered to obtain Example 1. Example 1 includes 1.0% by weight based on the total weight of Example 1 of units derived from ethylenediaminetetraacetic acid dianhydride.

As in Example 1, Example 2 was prepared. The reaction product of polyol and ethylenediaminetetraacetic dianhydride was changed. The difference was that polyol #1 (99 grams) was used instead of the polyester polyol synthesized in the laboratory. Example 2 includes 1.0% by weight based on the total weight of Example 2 of units derived from ethylenediaminetetraacetic acid dianhydride.

A variety of characteristics were measured for Example 1-2 and the polyester polyol synthesized in the laboratory. The OH number is determined according to ASTM E 1899-08; the acid value is determined according to ASTM D4274-16; the number average molecular weight (M _n ) and the weight average molecular weight (M _w ) are described as follows by SEC analysis. Each sample (0.01 g) was dissolved in tetrahydrofuran (4.0 mL) to obtain the sample concentration (2.5 mg/mL). Separation module: Waters e2695; Column: Polymer Labs PLGel Mixed E column (Polymer Labs PLGel Mixed E column) × 2, 3 µm particle size and mixed C column × 1, 5 µm Particle size; column temperature: 40℃; eluent: tetrahydrofuran (unstable); flow rate: 1 mL/min; injection volume: 50 µL; analysis time: 40 minutes; detector: Waters 2414 refractive index detector (Waters 2414 Refractive Index Detector) (40℃); Calibration: Agilent Technologies Polystyrene (PS)-Medium EasiVials (Agilent Technologies Polystyrene (PS)-Medium EasiVials), batch number 0006386106; Software: Agilent (Agilent) OpenLAB CDS (EZChrome) Version) Type A.04.06.

The results are reported in Table 1 in Table 1 Example 1 Example 2 Polyester polyol synthesized in the laboratory Number of OH (mg KOH.g) 66 51 67 Acid value (mg KOH/g) 4.8 8.8 0.4 Number average molecular weight 1840 - 1680 Weight average molecular weight 2700 - 3420 Molecular weight dispersion (M _w /M _n ) 2.01 - 2.04

The data in Table 1 shows that for Example 1-2, the reaction product of polyol and ethylenediaminetetraacetic dianhydride was prepared.

Example 3, a solvent-based composition was prepared as follows. Example 1, the solvent, and the components and amounts indicated in Table 2 were added to the container and mixed.

As in Example 3, Comparative Example A was prepared, and the changes in components and amounts are indicated in Table 2. Table 2 Example 3 Comparative example A The reaction product of polyol and ethylenediaminetetraacetic acid dianhydride (Example 5) 10.1 g - Polyester polyol synthesized in the laboratory - 10.2 grams MOR-FREE CR9-101 2.62g 2.64g MOR-FREE C-33 2.62g 2.64g Solid content in ethyl acetate (wt%) 29.6 30.2 Isocyanate index 1.2 1.2

The laminate was prepared using Example 3 as follows. Manual laminator with oil heating roller (clamping temperature of 150°F; running speed of 20 feet/minute n) and coating weight of about 1.05 lbs/ream. A laminate having a coating area of about 12 inches×10 inches was prepared one by one. Example 3 was formulated into ethyl acetate containing 35% by weight of solids, and then coated on the primary film; the coated primary film was oven dried (90° C.; about 1 minute). Then the coated primary film was laminated onto the secondary film with an oil-heated roller manual laminator (about 40 psi); then the laminate was cured at about 20°C for seven days.

As discussed above, Comparative Example A was used to prepare a laminate.

T-peel bonding strength test and retort bag test were performed on the laminate. The results are reported in Table 3.

The T-peel bond strength was measured on the Instron tensile tester with a 50 N load cell at a rate of 10 inches/minute to a 1-inch strip. Test three strips of each laminate, and record the high strength and average strength and failure mode. In the case of film tearing and film stretching, report the high value, and in other failure modes, report the average T-peel bond strength.

The retort bag test of the laminate was performed as follows. The cured laminate (9 inches × 11 inches) was folded to form a double layer, so that one layer of PE film was in contact with the other layer of PE film. Then trim the edges with a paper cutter to obtain a folded sheet (approximately 5 inches × 7 inches). The edges are then heat sealed to form a bag with an inner size of 4 inches x 6 inches. Then fill the bag with 100 mL of a sauce blend of ketchup, vinegar and vegetable oil in equal parts by weight through the open edge. After filling, the bag is sealed in a way that minimizes air entrapment inside the bag. Then place the filled bag carefully in boiling water and keep it submerged in water for 30 minutes or 60 minutes. When completed, compare the degree of tunneling, delamination or leakage with obvious pre-existing defects. table 3 Example 3 Comparative example A Primary film: PET/foil laminated film (coated foil side) Secondary film: polyethylene film T-Peel Bond Strength (Day 7) 267 + 3 g/25mm 148 + 8 g/25mm Failure mode Adhesive transfer (about the adhesive of the first film) Adhesive transfer (about the adhesive of the first film) Retort pouch (30 minutes) 72 + 3 g/25mm 22 + 4 g/25mm Retort bag failure mode Adhesive transfer (about the adhesive of the secondary film) Adhesive transfer (adhesive for secondary film) and delamination Primary film: Metallized PET film Secondary film: PET film T-Peel Bond Strength (Day 7) 105 + 12 g/25mm 74 + 9 g/25mm T-peel bond strength failure mode Adhesive transfer (about the adhesive of the secondary film) Adhesive transfer (about the adhesive of the secondary film)

The data in Table 3 shows that for the two laminates including the metallized film, Example 3 has an improved T-peel bond strength on the 7th day compared to Comparative Example A.

In addition, the data in Table 3 shows that for laminates including metallized films, Example 3 advantageously has an improved retort bag value at 30 minutes compared to Comparative Example A. The improved retort pouch value advantageously illustrates the greater adhesion strength of the sauce blend tested.

Example 4, a solvent-based formation, was prepared as follows. Example 2, the solvent, and the components and amounts indicated in Table 4 were added to the container and mixed.

As in Example 4, Comparative Example B was prepared, and the changes in components and amounts are indicated in Table 4. Table 4 Example 4 Comparative example B The reaction product of polyol and ethylenediaminetetraacetic acid dianhydride (Example 6) 10.00 g - Polyol #1 - 10.04g Ethyl acetate 30.1 grams 20.0 g MOR-FREE CR9-101 1.28g 0.60 g MOR-FREE C-33 1.28g 0.60 g Solid content in ethyl acetate (wt%) 38.6 34.9 Isocyanate index 1.2 1.2

As discussed above, Example 4 and Comparative Example B were used to prepare laminates.

As discussed above, the laminate was subjected to a T-peel bond strength test and a retort bag test. The results are reported in Table 5. table 5 Example 4 Comparative example B Primary film: PET/foil laminated film (coated foil side) Secondary film: polyethylene film T-Peel Bond Strength (Day 7) 330 + 7 g/25mm 285 + 6 g/25mm Failure mode Adhesive transfer (about the adhesive of the first film) Adhesive transfer (about the adhesive of the first film) Retort pouch (30 minutes) 28 + 8 g/25mm 10 + 3 g/25mm Retort bag failure mode Adhesive transfer (adhesive for secondary film) and delamination Adhesive transfer (adhesive for secondary film) and delamination Primary film: PET/foil laminated film (coated foil side) Secondary film: PET film T-Peel Bond Strength (Day 7) 121 + 4 g/25mm 87 + 3 g/25mm T-peel bond strength failure mode Adhesive transfer (about the adhesive of the secondary film) Adhesive transfer (about the adhesive of the secondary film)

The data in Table 5 shows that for two laminates including a metalized film, Example 4 has an improved T-peel bond strength on day 7 compared to Comparative Example B.

In addition, the data in Table 5 shows that for laminates including metallized films, Example 4 advantageously has an improved retort bag value at 30 minutes compared to Comparative Example B. The improved retort pouch value advantageously illustrates the greater adhesion strength of the sauce blend tested.

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no

Claims (8)

A solvent-based composition comprising: A reaction product made by reacting a polyol with an amino polycarboxylic acid compound; Isocyanate; and Solvent. The solvent-based composition of claim 1, wherein the amino polycarboxylic acid compound is an ethylene diamine tetraacetic acid compound. The solvent-based composition of claim 1, wherein the amino polycarboxylic acid compound is selected from the group consisting of ethylenediaminetetraacetic anhydride, ethylenediaminetetraacetic acid, and combinations thereof. The solvent-based composition of claim 1, wherein the reaction product has 0.03 to 10.0% by weight of units derived from the amino polycarboxylic acid compound based on the total weight of the reaction product. The solvent-based composition of claim 1, wherein the weight average molecular weight of the polyol is 300 to 12,000 g/mol. The solvent-based composition of claim 1, wherein the isocyanate index of the solvent-based composition is in the range of 0.9 to 1.6. The solvent-based composition of claim 1, wherein the solvent is 10% to 80% by weight of the solvent-based composition based on the total weight of the reaction product, the isocyanate, and the solvent. A laminate formed from the solvent-based composition according to any one of claims 1 to 7.